Azo compounds



Patented Apr. 10, 1945;

.lffUNlTED azo COMPOUNDS James G. McNally and Joseph B." Dickey, Roch-j ester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 26, 1943, Serial No. 492,444

6 Claims. (@1. 260-205) This invention relates to new azo compounds having the formula:

wherein R. represents a member selected from the group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, an allyl group, a fi-methoxyethyl group, a B-ethoxyethyl group, a fi-hydroxyethyl group, a e-hydroxypropyl group and a 'y-hydroxypropyl group, R represents a member selected from the group consisting of a B-hydroxyethyl group, a e-hydroxypropyl group, a -hydroxypropyl group, a eq-dihydroxypropyl group, a ,B-rnethoxyethyl group and a B-ethoxyethyl group and X represents a member selected from the group consisting of hydrogen and a methyl group. This invention also relates to textile materials colored with the aforesaid dyes.

The azo compounds of our invention constitute valuable dyes for colorationof textile materials such as organic derivatives of cellulose, wool, silk,

nylon, Vinyon and wool-like fibers derived.

from protein-like materials, such as casein wool. They are particularly of value for the coloration of cellulose acetate. Lacquers composed of cellulose esters, cellulose ether and vinyl derivatives, for example, also can be colored. Coloration can be effected by dyeing, printing, stencilling or other suitable means.

It is an object of our invention to provide a newclass of azo dyes. Another object of our in vention is to provide a process for the coloration of organic derivatives of cellulose, wool, silk, ny, lon and Vinyon textile materials. A further object is to provide colored textile materials which possess good fastness properties and which are readily discharged. A specific object is to provide colored cellulose acetate textile materials which have good fastness and dischargeability properties. Other objects will appear hereinafter.

Typical organic derivative of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate or cellulose butyrate and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose such' as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such as methyl cellulose, ethyl cellulose or benzyl cellulose.

The dyeings obtained with the dye compounds of our invention are characterized by exceptional light fastness and by. good fastness properties .to

gas fumes, Washing and perspiration. Further, the dye compounds of our invention possess g Q afiinity for the textile materials named and can. be applied rapidly thereto at relatively low temperatures. The advantages of the dye compounds appear to be realized to their greatest extent when cellulose acetate is the material to be colored.

The azo compounds of our invention can be prepared by diazotizing compounds having the formula: v

NOz-O-NHz H 0'= s N wherein R has the meaning previously assigned to it and coupling the diazonium compounds obtained withthe compounds having the formula:

wherein R1, R2 and X have the meaning previously assigned to them.

The following examples illustrate the preparation of the azo compounds ofour invention.

Example 1 500 cc. of sulfuric acid (9596%) were placed in a fiveliter flask fitted with a stirrer and ther mometer. 76 g. of sodium nitrite (dry) were added slowly with stirring over a period of 1 minute. The temperature of the sulfuric acid rose to '70? to 75 C, After the addition of the nitrite, the temperature fell to C. and. the reaction mixture was stirred until a clear solution ofnitrosyl sulfuric acid obtained. The solution was perature at about 20 C. The resulting mixture was cooled to 15 C. and 245 g. (1.0 mole) of 2- .amino 5 nitrobenzenesulfonethylamide were added simultaneously with 1 kg. of acetic acid, keeping the temperature at 15 C. The resulting mixture was stirred until solution was complete and then for about an additional hour. The mixture was poured into five liters of ice and: water and the precipitated diazonium complex (yellow) was filtered off and washed well with water.

207 g. (1 mole) of allyl glycerylaniline were dissolved in two liters of acetic acid and the diazonium complex was added to the solution with stirring. The resulting mixture was stirred for 12 hours. Water was then added to precipitate the azo dye which was filtered off, washed with water and dried. The azo' dye had the following formula:

It colored cellulose acetate pinkish-rubine shades which were fast to light. The term glyceryl as used herein is equivalent to the term B -dihydroxypropyl.

- Example 2 231 g. (1 mole) of 2-amino-5-nitrobenzene sulfonmethylamide was diazotized; with nitrosyl sulfuric acid exactly in Example 1. The diazonium complex was coupled with 221 g. (1 mole) of allyl glycerylaniline exactly as in Example 1. The resulting azo dye had the following formula:

H onz on-om Example 4 261 g. (1 mole) of 2-amino-5-nitrobenzenesulfon-c-hydroxyethylamide was diazotized with nitrosyl chloride exactly as in Example 1. The diazonium complex was coupled with 207 g. (1 mole) of allyl glycerylaniline'as in Example 1.

The resulting azo dye had the following formula:

/CH2-CH=GHI u O=iN H H II cnromon It dyed cellulose acetate pinkish-rubine shades, fast to light.

Amine Coupling component Color 1 3 -b o ethyl-amide Allyl-B-hydroxyethyl-m-toluidinc Pink. 2 2-amino-5-mtro-benzenesulfon-n-buty]-amide Allyl-dhydroxy y apflme D- 3 Allyl glyceryl-m-toluidmcn P nlnsh-rubme. 4 Allyl-fi-hydroxycthyl-m-tolul P nk 5 Allyl glyceryl aniline." Pinklsh-rubine. 6 Allyl glycerylm-toluidm Do. 7 Allyl-fl hydroxyethyl aniline Pink. 8 Allyl-B-hydroxypropyl aniline. Do. 9 yl-B-m oxyetliyl aniline Do. 10 Allyl-B, 7 diliydroxypropyl m-tolmdma. Pinkish-rubi no. u Allyl -hydroxypropyl m-toluidme Do. Allyl-B-hydroxyethyl aniline Pink. 13 Allyl-fl-hydroxyptopyl ani 11nc Do. 14 Allyl-B-methoxyethyl aniline Do. 15 Allyl B, -dihydroxy-propyl m -to luidmc. Imlnsh-r ubinc. 16 Allyl v-hydroxypropyl-ln toluidmc Do. 17 Ally] B-hydroxyethyl aniline Pink 18 Allyl ,s- -dihydroxypropyl m;t 1 e. Plnkish-rubme. 19 .r Allyl 'y-hydroxypropyl mtoluidme Do. 20 2-ammo-5-mtro-benzene sulfon-B-hydroxyethylamida Allyl fl-liydrnxy y $111111e l 21 Allylfl, -dihydroxy-propyl m -to1u1d1nc. Pmkish-rubine. 22 1 Allyl -hydroxypropyl m-toluidmc D0. 23 2-am no-5-n tro-benzene sulfonethyl-amide Allyl 18, 'y-dihydroxypropyl an l ne Do. 24 2'am no-fin tro-benzenesulfonmethyl amide Allyl B, -dihydroxypropylan1lrne Do. 25 2-am no-5-n tro-henzcnesulfonallylamide. Allylfl, -dihydroxypropylan li ne Do. 26 2-ammo-5-mtro-bcnzcnc sulion B-hydroxyctliyl a dc. Allyl B, 'y-dihydroxypropyl aniline D0.

of allyl glyceryl-m-toluidine exactly as in Example 1. The resulting azo dye had the followin formula: l

v CH2'CH=CH2 NOPON=N N/ I H CHz-CH--CH2 H: l 0=s-N OH on ll O CH:

It dyed cellulose acetate pinkish-rubine shades, fast to light.

Example 3 257 g. (1 mole) of 2-amino-5-nitrobenzenesulfonallylamide was diazotized with nitrosyl sulfuric acid exactly as in Example 1. The diazonium complex was coupled with 207 g, (1 mole) will be understood that the foregoing exwherein R has the meaning previously assigned to it can be prepared as indicated by the following equations: I

d Chlorsulfonic 1 acid NOrOCl also NO: 7 I and/r l I (POClz+PGl v SOsH Y Y alkali NO C1 N02- 'NH': NOr- NH:

' I alkylsulfate alkyl halide I H O=S C1 0:15-4:11, .alkylhalide O ll O 0 R Similarly, these compounds can also be prepared by the following indicated process steps.

NQr-QCI Y NH: NO2C1 NO2ONH2 l L 0=S N o= -N o R d \R Any other suitable methods can be employed.

In the first series. of equations, it will be understood that the amount of alkylating or allylating agent used determines whether one or both of the hydrogen atoms of the sulfonamide group is replaced by an alkyl or allyl group. In the present instance only sufiicient alkvlating or allylating agent necessary to replace one hydrogen atom should be used.

2-amino-5-nitrophenylsulfonamide, Z-amino- 5-niltrophenylmethylsulfonamide, 2-amino-5-nitrophenylethylsulfonamide and other similar type compounds can be prepared by the general method described by P. Fischer, Berichte der Deutschen Chemischen Gesellschaft, vol. 24, page 3790 (1891). The coupling components used in the preparation of the azo dye compounds of our invention can be prepared by methods-known to those skilled in the art. From the foregoing, the preparation of the components used in the manufacture of the .azo dye compounds will be clear to those skilled in the art.

It is here noted that the term nylon refers to a linear polyamide resin .which is believed to basically be described or claimed in U. S. Letters Patent 2,071,250, issued February 16, 1937, to 'Wallace H. Carothers. The term Vinyon refers to a vinyl chloride-vinyl acetate copolymer. This material is more completely identified, at pages 73 and 74 of Synthetic Organic Chemicalsjf th edition, published October 15, 1940,

Primary alkylaminc allylamine by Carbide & Carbon Chemicals Corporation.

The azo compounds of our invention are, for the most part, relatively insoluble in water and, accordingly, they may be advantageously directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding the dye to a paste in the presence of a sulfonated oil,soap or othersuitable dispersing agent and dispersing the result ing paste in water. In some instances, the dye may possess sufiicient solubility in wateras to render the use of a dispensing agent unnecessary. Generally speaking, however, the use of a dispersing agent is desirable.

Direct dyeing operations can, with advantage, be conducted at temperatures of about '75-85 C. but any suitable temperature may be used. Thus, the textile material to be dyed or colored is ordinarily added ,to thedyebath at a temperature lower than that'at which the main portion of the dyeing is to 'beefiected, a temperature approximating 45-55 C., for example, following which the temperature israised to! that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted may, of course,.be varied somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the art, the intensity of dyeing can be varied by varying the proportion of dye to material undergoing coloration. Generally speaking, 1-3 by weight of dye to material is employed although any desired proportions can be used.

Suitable dispersing agents together with the amounts that may be employed are disclosed in our Patent No. 2,115,030, issued April 26, 1938. The process disclosed in this patent for the dyeing of cellulose acetate silk can be used in applying the dyes of the present application to this material. I

It will be understood that the other textile materials named hereirrbefore can be directly colored from an aqueous dyebath in a similar manner as cellulose acetate silk. However, other suitable methods for the dyeing of these materials are known to those skilled in the art and these methods, of course, can be used in applying the dye compounds of this application if desired. We would further note that, while colors yielded by the dye compounds have been given primarily with reference to cellulose acetate silk, generally similar colors are ordinarily obtained on the other materials.

This application is a continuation-in-part of our copending application, Serial No. 426,056, filed January 8, 1942, now Patent No. 2,347,704.

What We claim as our invention and desire to be secured by Letters Patent of the United States is:

1. The azo compounds having the formula:

propyl group, a 'y-hydroxypropyl group, a c, y-

dihydroxypropyl group, a ,B-methoxyethyl group and a .s-ethoxyethyl group, and X represents a member selected from the group consisting of hydrogen and a methyl group.

2;;The azo compoundsheving the formula:

" CHPCH=CH1 whereinR, represents a, member selected from the group consisting of a. methyl group, an ethyl group, a, propyl group, a butyl group, an allyl group, a, fi-methoxyethyl group, a, fl-ethoxyethyl group, a p-hydroxyethyl group, a p-hydroxypropyl group and a yahydroxypropyi group, R

represents a, member selected from the group consisting of p-hydroxyethyl group, a. p-hydroxyp opy p, 'vyd yp opyl group, findihydroxypropyl group, a, ,B-methoxyethyl group anq a fl-ethoxyethyl group. 7

4. The 2.20 compound having the formula:

C Br- 0 H C H:

3 CzHs 5. The azo compound having the formula:

CHT-CHLTCHQ 6. The azo compound having the formula:

' GH:CH=CH1.

JAMES G. McNALLYu JOSEPH B. DICKEY. 

